JPS6018515A - Manufacture of polyurethane conformable to live body - Google Patents

Manufacture of polyurethane conformable to live body

Info

Publication number
JPS6018515A
JPS6018515A JP59100714A JP10071484A JPS6018515A JP S6018515 A JPS6018515 A JP S6018515A JP 59100714 A JP59100714 A JP 59100714A JP 10071484 A JP10071484 A JP 10071484A JP S6018515 A JPS6018515 A JP S6018515A
Authority
JP
Japan
Prior art keywords
adduct
hand
macrodiol
mixture
chain
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP59100714A
Other languages
Japanese (ja)
Other versions
JPH0410892B2 (en
Inventor
ゲルハルト・ヴイツク
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akzo NV
Original Assignee
Akzo NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akzo NV filed Critical Akzo NV
Publication of JPS6018515A publication Critical patent/JPS6018515A/en
Publication of JPH0410892B2 publication Critical patent/JPH0410892B2/ja
Granted legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L33/00—Antithrombogenic treatment of surgical articles, e.g. sutures, catheters, prostheses, or of articles for the manipulation or conditioning of blood; Materials for such treatment
    • A61L33/06—Use of macromolecular materials
    • A61L33/068—Use of macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/24—Heart valves ; Vascular valves, e.g. venous valves; Heart implants, e.g. passive devices for improving the function of the native valve or the heart muscle; Transmyocardial revascularisation [TMR] devices; Valves implantable in the body

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 本発明は、脂環状ジイノシアネーＩ・、脂肪族及び／又
は脂環状マクロジオール及び低分子−の脂肪族及び／又
は脂環状ジオールな基質とし、場合により溶剤に溶解し
ている生体に適合するポリウレタン及びその製造法に関
する。DETAILED DESCRIPTION OF THE INVENTION The present invention uses alicyclic diinocyane I, an aliphatic and/or alicyclic macrodiol, and a low molecular weight aliphatic and/or alicyclic diol as a substrate, optionally dissolved in a solvent. This invention relates to polyurethane that is compatible with living organisms and a method for producing the same.

従来の技術 ポリウレタンは既に公知であり、多クツ）方７人で製造
される。このようにして、例えばマクロジオールをジイ
ンシアネ−１・と反応させて４　（−１加物にし、この
手付加物を、１種又はＦｔ　ｆｊＪｊの低分子のジオー
ルで連鎖を延長することかてきる。。Prior art polyurethanes are already known and are produced in multiple ways. In this way, for example, a macrodiol can be reacted with diincyane-1 to form a 4(-1 adduct), and this hand adduct can be chain-extended with one or a low molecular weight diol of Ft fjJj. ..

ジイソシアネート、マクロジオール及び連ｉｔ’ｌ　ｆ
ｒＥ長剤を同時にいわゆる一浴法によって反応さ杖るこ
とも可能である。Diisocyanates, macrodiols and combinations
It is also possible to react the rE lengthening agent at the same time by the so-called one-bath method.

ポリウレタンは、他のプラスチックに比して比較的生体
に適合する、即ち人体及び動物の身体に十分に受入１１
られる、つまり身体と相容性であることによってすぐれ
ている。殊にポリウレタンは血液及び組織と相容性であ
る。Polyurethane is relatively biocompatible compared to other plastics, i.e., it is well accepted by the human and animal bodies.
It is excellent because it is compatible with the body, that is, it is compatible with the body. In particular, polyurethanes are compatible with blood and tissue.

しかしながら、従来公知の生体に適合するポリウレタン
は、なお多くの欠点を有する。このように、加水分解の
影響によって成程度短かい時間の間に機械的性質、例え
ば強度、伸び及び弾性は不利な影響をうけ、多くの、ｄ
　ＩＪウレタンは時間の経つうちにむしろ完全に分解す
る。However, the previously known biocompatible polyurethanes still have a number of drawbacks. Thus, mechanical properties such as strength, elongation and elasticity are adversely affected over a short period of time due to the effects of hydrolysis, and many d
IJ urethane rather completely decomposes over time.

前記のこれらの欠点は、か〜るポリウレタンからなる場
合には、生体に適合する成形体でも欠点が認められる。These drawbacks mentioned above are observed even in biocompatible molded products when made of such polyurethane.

更に、人工血管を、ホース又は薄い小管の形でポリマー
溶液からファイバーを紡糸し、運送し、ファイ、Ｓ−を
ロッド状台に置いてフリスにすることによって製造する
ことは公知である。Furthermore, it is known to produce vascular grafts by spinning and transporting fibers from a polymer solution in the form of hoses or thin tubules and placing the fi, S- on a rod-like platform to make a frizz.

このようにして、例えばヨーロツノξ特許第５０３５号
明１１１１書には、ボ１」マー溶液を、いわゆる静電紡
糸法によって紡糸する方法が記載されている。この人工
血管を製造するだめの紡糸液としては、多くのポリマー
、例えシ、し］：’　ＩＪアミド゛、ポリアクリルニト
リル及びポリウレタンがず入められる。分散液として加
工することのできるポリマー、例えばポリテトラフルオ
ルエチレンも、このヨーロッノξ特許明細書の方法によ
って加工することができる。In this way, for example, Yorotsuno ξ Patent No. 5035, Mei 1111 describes a method of spinning a 1'' polymer solution by the so-called electrostatic spinning method. A number of polymers, such as IJ amide, polyacrylonitrile, and polyurethane, are included in the spinning solution for producing this artificial blood vessel. Polymers which can be processed as dispersions, such as polytetrafluoroethylene, can also be processed by the method of this European ξ patent.

１イッ公開特許第２８０６０３７号明細１１１には、人
工血管を、ポリマー溶液からファイバーをスプレーして
形成するか〜る人工血管の池の製造法が記載されている
。この公開特許明細書には、実施例に種々のポリウレタ
ンが記載されている。この方法の場合にも、ポリウレタ
ンの前記欠点が認められる。No. 1, published patent application No. 2,806,037, specification 111, describes a method for producing an artificial blood vessel pond by spraying fibers from a polymer solution. This published patent specification describes various polyurethanes in the Examples. In this method as well, the aforementioned disadvantages of polyurethane are observed.

人工血管の製造技術を種々の方法によって、例えばファ
イ・々−を製造し、これを四ツ１上に置いてフリスにす
るか又は溶液な押出成形によって開発する場合には、人
工血管の挙動は、人体又は動物の身体ではポリマーを加
工する際に使用する技術によるだけではなく、ポリマー
それ自体、ポリマーの化学的構造及び特に製造法も決定
的に重要である。If the manufacturing technology of vascular grafts is developed by various methods, e.g., by manufacturing fibers, placing them on a 4-piece to make frills, or by solution extrusion, the behavior of the vascular grafts is , in the human or animal body, is of decisive importance not only by the technology used to process the polymer, but also by the polymer itself, the chemical structure of the polymer and especially the method of production.

従って、なお簡単で有利な方法で加工して生体に適合す
る成形体を得ることができ、経済的に得られ、殊に人体
及び動物の身体で太き（・安定性ですぐれているポリウ
レタンによる要求が存在する。Therefore, it is still possible to process in a simple and advantageous manner to obtain biologically compatible molded bodies, which are economically obtainable and especially suitable for use in the human and animal bodies. A request exists.

問題点を解決するための手段 それ故、本発明の目的はか＼るポリウレタンを得ること
である。この目的は、脂環状ジイソシアネート及び脂肪
族及び／又は脂環状マクロジオールを、溶剤が存在しな
いで反応させて手付加物にし、その際マクロジオール１
モル当りジイソシアネ−１・３〜２２モルを使用し、得
られた手利加物を、低分子の脂肪族及び／又は脂環状ジ
オール及び脂肪族及び／又は脂環状マクロジオールから
なる混合物で連鎖を延長し、その際手付加物を、ＮＣＯ
基対基調連鎖延長剤混合物Ｈ基のモル比１．１５：’Ｌ
〜１．０１：１で使用する方法によって解決される。Means for solving the problem It is therefore an object of the present invention to obtain such a polyurethane. The aim is to react alicyclic diisocyanates and aliphatic and/or alicyclic macrodiols in the absence of solvents to form hand adducts, with the macrodiols 1
Using 1.3 to 22 moles of diisocyanate per mole, the obtained additive is chain-extended with a mixture consisting of a low-molecular aliphatic and/or alicyclic diol and an aliphatic and/or alicyclic macrodiol. At that time, the hand appendage is
Molar ratio of base to base chain extender mixture H groups 1.15:'L
~1.01:1 is solved by the method used.

本発明方法を実施するためには、先づ脂肪族及び／又は
脂環状マクロジオールを、脂環状ジイソシアネートと溶
剤が存在しないで反応させて手付加物にする。脂環状ジ
イソシアネートはマクロジオールに対して過剰量で使用
するので、反応後に付加生成物と共に、なお遊離ジイソ
シアネートも存在する。To carry out the process of the invention, first an aliphatic and/or cycloaliphatic macrodiol is reacted with a cycloaliphatic diisocyanate in the absence of a solvent to form a hand adduct. Since the alicyclic diisocyanate is used in excess relative to the macrodiol, free diisocyanate is still present along with the addition product after the reaction.

手付加物を得るための脂肪族及び／又は脂環状マクロジ
オールとしては、ポリエーテルグリコール、ポリカーｓ
ｒネート、例えばポリへギザメチレンカーゼネ−１・〔
バイエル社製のデスモア　ｘ　７　（Ｄｅｓｍｏｐｈｅ
ｎ　）　２０２０　］及びＯＨ末端基２個を有する他の
、（Ｆ　ＩＪママ−適当である。しかしながら本発明方
法の特に好ましい実施形式では、平均分子量（重量平均
値）ＭＷ６００〜約２０００を有するポリテトラメチレ
ングリコールを使用する。Aliphatic and/or alicyclic macrodiols for obtaining hand adducts include polyether glycols, polycarbons
r-nate, such as polyhedazamethylene carzene-1.[
Desmophe x 7 manufactured by Bayer
n ) 2020 ] and other (FIJ moms) with two OH end groups are suitable. However, in a particularly preferred embodiment of the process according to the invention, polytetra Use methylene glycol.

脂環状ジイソシアネートとしては、好ましくは４，４′
−ジシクロヘキシルメタンジイソシアネー］・、殊に市
場で得られるその異性体混合物、トランス形及びシス形
のシクロヘキサンジイソシアネー）−１，４並びに１−
ランス形とシス形との混合物を使用する。４，４′−シ
ンクロヘキシルメタンジイソシアネートとシクロヘキサ
ンジインゾアネートー（１，４）とからなる混合物も適
当である。The alicyclic diisocyanate is preferably 4,4'
-dicyclohexylmethane diisocyanate], in particular its isomer mixtures obtained on the market, cyclohexane diisocyanate in trans and cis form)-1,4 and 1-
A mixture of lance and cis forms is used. Mixtures of 4,4'-synchrohexylmethane diisocyanate and cyclohexane diinzoanate (1,4) are also suitable.

手付加物を製造する場合、触媒の使用は一般に不必要で
ある。When making hand adducts, the use of catalysts is generally unnecessary.

手付加物は、炭素原子２〜８個を有する低分子の脂肪族
及び／又は脂環状ジオール及び脂肪族及び／又は脂環状
マクロジオールを含有する連鎖延長剤からなる混合物で
連鎖を延長する。連鎖延長剤としては、特にブタンジオ
ール−（１゜４）とポリテトラメチレングリコールとか
らなり平均分子量Ｍｗ＝６００〜２０００を有する混合
物が適当である。Hand adducts extend the chain with a mixture of chain extenders containing low molecular weight aliphatic and/or cycloaliphatic diols having 2 to 8 carbon atoms and aliphatic and/or cycloaliphatic macrodiols. As the chain extender, a mixture of butanediol (1°4) and polytetramethylene glycol having an average molecular weight Mw of 600 to 2000 is particularly suitable.

本発明の脂肪族及び／又は脂環状ジオール又はマクロジ
オールとは、脂肪族基又は脂環状基だけか又は脂肪族基
並びに脂環状基を有するジ、ｔ−ルテする。マクロジオ
ール及び低分子のジオールとしては、脂肪族又は脂環状
の化合物を使用する。それというのもこの化合物は、周
知のように例えば芳香族物質に比較してわずかな化学的
反応性及びすぐれた耐光性を有し、医学用の使用の場合
には低い化学的反応性に重きを置かなげねばならないか
らである。The aliphatic and/or alicyclic diol or macrodiol of the present invention is a di-, t-lute diol having only an aliphatic group or an alicyclic group, or an aliphatic group and an alicyclic group. As the macrodiol and the low-molecular diol, aliphatic or alicyclic compounds are used. This is because, as is well known, these compounds have a low chemical reactivity and a good light resistance compared to, for example, aromatic substances, and in the case of medical use, importance is placed on low chemical reactivity. This is because you have to leave it behind.

すぐれたブタンジオールと共に、なかんずく次のジオー
ルを連鎖延長剤混合物で使用することができる：ネオベ
ンチルグリコール、エチレングリコール、プロ／ξンジ
オールー（１，３）及びヘキサンジオール−（１，６）
。Along with the preferred butanediol, inter alia the following diols can be used in the chain extender mixture: neobentyl glycol, ethylene glycol, pro/ξ diol-(1,3) and hexanediol-(1,6).
.

好ましくは、連鎖の延長は触媒の存在で行なう。適当な
触媒は、殊に有機錫化合物、例えばジブチル錫ジラウレ
ート、ジブチル錫ジオクトエートその他である。Preferably, chain extension is carried out in the presence of a catalyst. Suitable catalysts are, in particular, organotin compounds, such as dibutyltin dilaurate, dibutyltin dioctoate, and the like.

連鎖の延長は、同じようにして溶剤が存在しないで行な
ってもよい。１種又は数種の溶剤の存在で作業すること
もできる。好ましい溶剤には、例えばジメチルアセトア
ミド又はジメチルホルムアミドが所属する。溶剤を有し
ない作業の場合には、手付加物と連鎖延長剤混合物との
好ましい混合物を調製するのが有利であり、その際両成
分を重量比７０：３０〜３０　：　７０　、特に６０：
４０〜４０二６０、殊に５５：４５〜４５：５５で混合
する。Chain extension may be carried out in the same manner without the presence of a solvent. It is also possible to work in the presence of one or more solvents. Preferred solvents include, for example, dimethylacetamide or dimethylformamide. In the case of work without solvents, it is advantageous to prepare preferred mixtures of hand adduct and chain extender mixture, the two components being in a weight ratio of 70:30 to 30:70, in particular 60:
Mix at a ratio of 40 to 40 to 60, especially 55:45 to 45:55.

混合後にガスを抜き、反応させる。反応は高温度、例え
ば８０℃で行なってもよい。硬化とも呼ばれる工程は、
３日又は数日まで行なうことができ／る。After mixing, remove the gas and allow the mixture to react. The reaction may be carried out at elevated temperatures, for example 80°C. The process, also called curing,
It can be done for up to three days or several days.

を 次（・で得られた。ＨＰ　ＩＪウレタンは加工して顆粒
にし、任意に長時間保存することができる。The HP IJ urethane can be processed into granules and stored for an optionally long period of time.

連鎖の延長を溶剤中で行なう場合には、ポリウレタンは
水に沈澱させて分離し、乾燥することができる。If the chain extension is carried out in a solvent, the polyurethane can be separated by precipitation in water and dried.

溶液で生じたポリウレタンを溶液でそのま〜にしておき
、更に溶剤を添加して直ちに加工することのできる適当
な粘度の溶液を製造することもできる。It is also possible to leave the solution-formed polyurethane in solution and add more solvent to produce a solution of a suitable viscosity that is ready for processing.

本発明によって製造したポリウレタンは公知方法によっ
て加工して生体に適合した成形体、例えば人工血管、カ
テーテル、血液ポンプ、心弁膜及び血液を通す中空器官
、例えば管、耳形成体、ゾンデの保護皮その他にするこ
とができる。このようにして、ポリウレタンはその融液
の押出成形により成形することができる。The polyurethane produced according to the present invention can be processed by known methods to produce molded bodies compatible with living organisms, such as artificial blood vessels, catheters, blood pumps, heart valves, and hollow organs through which blood passes, such as tubes, otoplasts, protective skins for probes, etc. It can be done. In this way, polyurethane can be molded by extrusion of its melt.

特別の注出技術では手付加物は適当量の連鎖延長剤と混
合し、ガスを抜いた後に、予め調製した型に注入するこ
とができる。硬化後に、型どおりの押付は成形体が得ら
れ、これはテフロン又はシリコンの型から容易に取出す
ことができる。この作業法による好ましい使用分野は、
血液ポンプ及び耳形成体である。In a special pouring technique, the hand additive can be mixed with an appropriate amount of chain extender, degassed, and then poured into a pre-prepared mold. After curing, the mold-like pressing results in a molded body, which can be easily removed from the Teflon or silicone mold. The preferred fields of use for this working method are:
Blood pump and otoplast.

ラッカー又は生体に適合する被膜を製造するためには、
ポリウレタンを溶剤の塩化メチレン、アセトン、クロロ
ホルム、トリクロルエチレン、テトラヒドロフラン、ジ
オキサン、ｎ−プロノミノール、シクロヘキザノール、
ジメチルホルムアミド又はジメチルアセトアミＰに室温
でとかして５重量％の溶液にし、シンｆの被膜に使用す
る。To produce lacquers or biocompatible coatings,
Polyurethane with solvents such as methylene chloride, acetone, chloroform, trichloroethylene, tetrahydrofuran, dioxane, n-pronominol, cyclohexanol,
It is dissolved in dimethylformamide or dimethylacetamide P at room temperature to make a 5% by weight solution and used for coating Synf.

人工血管に加工するためには１，４９１）ウレタンは好
ましくは溶解して使用し、公知方法で加工して人工血管
にし、その際好ましくは溶液を加工してファイ・ζ−に
し、次いでこれをロッドにフリスの形で置く。かＮる方
法は、例えばヨーロツ・ξ特許第５０３５号明細書及び
米国特許第４０４’　４４０４号明細書に記載されてし
・る。これらの明細書に記載の方法は、ファイ・Ｓ−を
静電場を利用して製造する方法である。For processing into artificial blood vessels, 1,491) Urethane is preferably used in a dissolved form and processed into artificial blood vessels by known methods, preferably by processing the solution into phi-ζ-, which is then Place it on the rod in the form of frizz. Such methods are described, for example, in European Patent No. 5035 and US Pat. No. 404'4404. The methods described in these specifications are methods for producing Phi S- using an electrostatic field.

か＼る人工血管を製造する他の好まし℃・適当な方法は
、ドイツ公開特許第２８０６０３０号明細書に記載され
ている。Another preferred and suitable method for producing such a vascular graft is described in DE 28 06 030.

特に本発明によるポリウレタンはこの方法で加工して人
工血管にすることができ、これは内移植して１２ケ月以
上の滞留時間後にも実際にその機械的及び物理的性質の
ロスを示さな（・ことは驚異的なことであった。更に、
このファイ・８−をドイツ公開特許第２８０６０３０号
明細書に記載されているようないわゆるファイ・ζ−ス
プレーによって加工する場合に、いわゆるゝゝ接芽の形
成〃を著しく下げることができることは驚異的なことで
あった。接芽の形成又は非ファイバー状の小さなかたま
りの形成とは、ロッドで得られたフリスにおける厚い個
所であり、これは紡糸液中の粘度差に基づいて、形成す
るファイバーに対して異なる蒸発が行われ、それ故これ
らの接芽又は小さなかたまりが形成することに帰因する
。In particular, the polyurethane according to the invention can be processed in this way into artificial blood vessels, which show virtually no loss of their mechanical and physical properties even after a residence time of more than 12 months after implantation. This was astonishing.Furthermore,
It is surprising that when this Phi-8- is processed by the so-called Phi-ζ-spray as described in German Published Patent Application No. 2806030, the so-called "formation of buds" can be significantly reduced. That was the case. Grap formation, or non-fibrous cluster formation, is a thick spot in the rod-produced fris that results in differential evaporation of the forming fibers based on viscosity differences in the spinning solution. , and is therefore attributed to the formation of these apical buds or small clusters.

実施例 例１ 攪拌器、窒素導入管及び導出管を有する冷却器を備えて
いる二頭フラスコ中に、４，４′−ジシクロヘキシルメ
タンジイノシアネー）　１１Ｖａｌ及び無水ポリテトラ
メチレングリコール（Ｍｗｌｏｏｏ　）　１．５　Ｖａ
ｌを装入シ、絶工ｆ　Ｊ’ｔｔ、拌Ｌ　ｊ；　カーら１
２０℃で３時間加熱する。手付加物を製出するだめの付
加反応を、理論的に割算したイノシアネート含量１８．
２重量％が得られるまで続ける。その間に連鎖延長剤を
製出するために、無水ブタンジオール＝（１，４）　４
．５　Ｖａｌ及び無水ポリテトラメチレングリコール（
Ｍ　１０００）４５Ｖａｌを、錫触媒（ジブチル錫ジラ
ウレート５ｍｇ／連鎖延長剤の全量１００Ｓ’）を有す
る別の密封容器中で攪拌しながら混合する。必要な場合
には、この混合を若干加熱（約５０℃）して行なうこと
ができる。ポリウレタンを製造するためには、手利加物
４６．７５ｆを連鑓延長剤５３２５Ｉｉ′と一緒にして
混合温度５０℃で攪拌し、ガスを抜き、硬化型中に注入
する。８０℃で３日間硬化後に、相対粘度（ジノチルホ
ルムアミ１？にとかした１重量％）３．０５６を測定す
る。Example 1 In a two-headed flask equipped with a stirrer, a condenser with a nitrogen inlet and an outlet, 4,4'-dicyclohexylmethanediinocyane (11 Val) and anhydrous polytetramethylene glycol (Mwlooo) 1. 5Va
Charge L, Zekko f J'tt, Stir L j; Carr et al. 1
Heat at 20°C for 3 hours. The inocyanate content, calculated by theoretically dividing the addition reaction to produce the hand adduct, is 18.
Continue until 2% by weight is obtained. In the meantime, to prepare a chain extender, anhydrous butanediol = (1,4) 4
．． 5 Val and anhydrous polytetramethylene glycol (
M 1000) 45 Val are mixed with stirring in a separate sealed vessel with a tin catalyst (5 mg dibutyltin dilaurate/total amount of chain extender 100 S'). If necessary, this mixing can be carried out with some heat (approximately 50° C.). To produce the polyurethane, the filler material 46.75f is mixed with the chain extender 5325Ii', stirred at a mixing temperature of 50 DEG C., degassed and poured into a curing mold. After curing for 3 days at 80° C., a relative viscosity (1% by weight dissolved in dinotylformamide 1?) of 3.056 is determined.

ポリウレタンのショアＡ−硬度は８０であり、軟化範囲
は約　１２５℃であり、融解範囲は約１８５℃である。The polyurethane has a Shore A hardness of 80, a softening range of about 125°C, and a melting range of about 185°C.

、Ｉ？　リウレタンは透明無色である。,I? Urethane is transparent and colorless.

ポリウレタンは、臀部のアセトノ、塩化メチレン及びク
ロロホルムからなる溶剤混合物の５重量％の溶液の形で
、ドイツ公開特許第２８０６０３０号明細書によるノア
イノζ−スプレーによって加工することができる。The polyurethane can be processed by NOINO ζ-spray according to DE 28 06 030 in the form of a 5% strength by weight solution of a solvent mixture consisting of acetonate, methylene chloride and chloroform.

例２〜８ 同じ作業法で１．ｄ　ＩＪウレタンを次表に記載の原料
から製造した：Examples 2-8 Same working method 1. d IJ urethane was manufactured from the raw materials listed in the following table:

Claims (1)

【特許請求の範囲】 １、　ジイソシアネートとジオールとを反応させて予イ
τ１加物にし、手付加物を連鎖延長剤からなる混合物で
連鎖を延長して生体に適合するポリウレタンを製造する
方法において、脂環状ジイソシアネート及び脂肪族及び
／又は脂環状マクロジオールを、溶剤が存在しないで反
応させて手付加物にし、その際マクロジオール１モル当
りジイソシアネート３〜２２モルを使用し、得られた手
付加物を、低分子の脂肪族及び／又は脂環状ジオール及
び脂肪族及び／又は脂環状マクロジオールからなる混合
物で連鎖を延長し、その際手付加物を、ＮＣＯ基対連鎖
延１そ剤混合物のＯＨ基のモル比１．１５−１〜１．０
１　：　１で使用することを特徴とする、生体に適合す
る。４ｑ　ＩＪウレタンの製造法。 ２　マクロジオール１モル当りジイソシアネート６．５
〜８モルを特徴する特許請求の範囲第１項記載の方法。 ３、手付加物を、ＮＣＯ基対連鎖延長剤混合物のＯＨ基
のモル比１．０７　：　１〜１．０４　：　ｌで使用す
る、特許請求の範囲第１項又は第２項記載の方法。 屯　手付加物を形成するために平均分子ｆｉｔ　Ｍｗ６
００〜２０００を有する７１？リテトラメチレングリコ
ールを使用し、連鎖を延長するためにブタンジオール−
（１゜２）とポリテトラメチレングリコールとからなる
混合物を特徴する特許請求の範囲第、１項から第３項ま
でのいず旧か１項に記載の方法。 ５、　マクロジオールとしてボ゛リカー７１？不−１・
を特徴する特許請求の範囲第１項から第５項までのいず
れか１項に記載の方法。 ６、脂環状ジイソシアネートとして、４．４’−ジシク
ロヘキシルメタンジイソノアネ−１・を特徴する特許請
求の範囲第１項から第５項までのいづれか１項に記載の
方法。 ７　脂環状シイノンアネートとして、シクロへキザノジ
Ａノシアネー１−−（１，４）を使用スる、特許請求の
範囲第１項から第５項までのいず」しか１項に記載の方
法。 ８．４．４’−ジシクロヘキシルメタンジイノシアネ−
１・を、シクロヘキサンジイソシアネートと混合して使
用する、特許請求の範囲第６項記載の方法。 ９、予ｆ：ｊ加物と連謂延長剤混合物とを、重量比３０
ニア０〜７０’：３０で反応させる、特許請求の範囲第
１項から第８項までのいずれか１項に記載の方法。 １０　重量比６０：４０〜４０：６０で反応させる、特
許請求の範囲第９項記載の方法。 １１　有機ｍ剤に溶解したポリウレタンの粘度を０２〜
７，５　Ｐａ、ｓに調節する、特許請求の範囲第１項か
ら第１０項までのいずれか１項に記載の方法。 １２、有機溶剤として塩化メチレン、アセトン、クロロ
ホルム、トリクロルエチレン、テトラヒドロフラン、ジ
オキサン、ｎ−ゾロパ′ノール、シクロヘキサノール、
ジメチルポルムアミド、ジメチルアセトアミドからの１
４重文（、主数種を特徴する特許請求の千α囲り）１項
カ汀）第１１項まで、のいずれか１項に記載の方法１．[Claims] 1. A method for producing biocompatible polyurethane by reacting a diisocyanate and a diol to form a pre-tau adduct, and extending the chain of the hand adduct with a mixture of a chain extender, comprising: A cycloaliphatic diisocyanate and an aliphatic and/or cycloaliphatic macrodiol are reacted to form a hand adduct in the absence of a solvent, using from 3 to 22 mol of diisocyanate per mol of macrodiol, and the resulting hand adduct is chain-extended with a mixture consisting of a low-molecular aliphatic and/or alicyclic diol and an aliphatic and/or alicyclic macrodiol, in which the hand adduct is separated from the NCO group by the OH of the chain-spreading agent mixture. Molar ratio of groups 1.15-1 to 1.0
It is characterized by being used in a ratio of 1:1 and is compatible with living organisms. 4q Method for producing IJ urethane. 2 6.5 diisocyanates per mole of macrodiol
2. A method according to claim 1, characterized in that .about.8 mol. 3. Process according to claim 1 or 2, in which the hand adduct is used in a molar ratio of NCO groups to OH groups of the chain extender mixture of 1.07:1 to 1.04:1. The average molecule fit Mw6 to form a tun hand adduct
71 with 00-2000? using ritetramethylene glycol and butanediol for chain extension.
A method according to any one of claims 1 to 3, characterized in that the mixture consists of (1°2) and polytetramethylene glycol. 5. Bolicar 71 as a macrodiol? F-1・
A method according to any one of claims 1 to 5, characterized in that: 6. The method according to any one of claims 1 to 5, wherein the alicyclic diisocyanate is 4,4'-dicyclohexylmethane diisonoane-1. 7. The method according to any one of claims 1 to 5, wherein cyclohexanodianocyane 1--(1,4) is used as the alicyclic cyinone anate. 8.4.4'-Dicyclohexylmethanediinocyane-
7. The method according to claim 6, wherein 1. is used in admixture with cyclohexane diisocyanate. 9. Pref:j Additive and so-called extender mixture at a weight ratio of 30
9. The method according to claim 1, wherein the reaction is carried out at a ratio of 0 to 70':30. 10. The method according to claim 9, wherein the reaction is carried out at a weight ratio of 60:40 to 40:60. 11 The viscosity of polyurethane dissolved in organic m-agent is 02~
7.5 Pa, s. 12. Organic solvents such as methylene chloride, acetone, chloroform, trichloroethylene, tetrahydrofuran, dioxane, n-zolopanol, cyclohexanol,
1 from dimethylpolamide, dimethylacetamide
The method according to any one of 1.
JP59100714A 1983-05-21 1984-05-21 Manufacture of polyurethane conformable to live body Granted JPS6018515A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19833318730 DE3318730A1 (en) 1983-05-21 1983-05-21 Biocompatible polyurethanes
DE3318730.4 1983-05-21

Publications (2)

Publication Number Publication Date
JPS6018515A true JPS6018515A (en) 1985-01-30
JPH0410892B2 JPH0410892B2 (en) 1992-02-26

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ID=6199696

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US (1) US5109077A (en)
JP (1) JPS6018515A (en)
DE (1) DE3318730A1 (en)
FR (1) FR2546170B1 (en)
IT (1) IT1179375B (en)

Families Citing this family (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE124072T1 (en) * 1985-01-04 1995-07-15 Thoratec Lab Corp METHOD FOR PRODUCING A MOLDED PART WITH SHAPE MEMORY PROPERTIES AND SOME OF THESE MOLDED PARTS OBTAINED.
US5506300A (en) * 1985-01-04 1996-04-09 Thoratec Laboratories Corporation Compositions that soften at predetermined temperatures and the method of making same
DE3600217A1 (en) * 1985-01-07 1986-09-04 Kurt Dr.-Ing. 7148 Remseck Ziesche First-aid device for heart attacks
US4621113A (en) * 1985-10-07 1986-11-04 The Dow Chemical Company Repeating block, oligomer-free, polyphase, thermoformable polyurethanes and method of preparation thereof
DE3539243A1 (en) * 1985-11-05 1987-05-21 Manfred Rycyk Puncturing cannula
DE3643465A1 (en) * 1986-12-19 1988-07-07 Akzo Gmbh Biocompatible polyurethanes
DE3841043A1 (en) * 1988-12-06 1990-08-02 Spuehl Ag Moulding containing cork, and process and apparatus for the production thereof
US5034461A (en) * 1989-06-07 1991-07-23 Bausch & Lomb Incorporated Novel prepolymers useful in biomedical devices
US5229431A (en) * 1990-06-15 1993-07-20 Corvita Corporation Crack-resistant polycarbonate urethane polymer prostheses and the like
EP0548256A4 (en) * 1990-09-12 1993-07-07 Polymedica Industries, Inc. Biostable polyurethane products
US5375609A (en) * 1992-01-27 1994-12-27 Medtronic, Inc. Pacing lead insulator
US5419921A (en) * 1993-03-22 1995-05-30 Medtronic, Inc. Pacing lead insulator
IT1276342B1 (en) * 1993-06-04 1997-10-30 Ist Naz Stud Cura Dei Tumori METAL STENT COVERED WITH BIOCOMPATIBLE POLYMERIC MATERIAL
US6140452A (en) * 1994-05-06 2000-10-31 Advanced Bio Surfaces, Inc. Biomaterial for in situ tissue repair
US20050043808A1 (en) * 1994-05-06 2005-02-24 Advanced Bio Surfaces, Inc. Knee joint prosthesis
DE19504414C2 (en) * 1995-02-10 1996-12-05 Pharmacia Gmbh Hose for a medical container
AUPO251096A0 (en) * 1996-09-23 1996-10-17 Cardiac Crc Nominees Pty Limited Polysiloxane-containing polyurethane elastomeric compositions
DE19640552A1 (en) * 1996-10-01 1998-04-02 Bayer Ag Process for improving the biocompatibility of thermoplastic polyurethanes
EP1230902A1 (en) * 1996-11-15 2002-08-14 Advanced Bio Surfaces, Inc. Biomaterial system for in situ tissue repair
US6111052A (en) 1997-04-30 2000-08-29 Medtronic, Inc. Polyurethane and polyurea biomaterials for use in medical devices
US6400992B1 (en) 1999-03-18 2002-06-04 Medtronic, Inc. Co-extruded, multi-lumen medical lead
GB9915932D0 (en) * 1999-07-08 1999-09-08 Sterilox Med Europ Ltd Oxidation-resistant endoscope coatings
EP1315470B1 (en) 2000-08-28 2009-07-15 Disc Dynamics, Inc. System for mammalian joint resurfacing
US20020183824A1 (en) * 2001-05-09 2002-12-05 Medtronic, Inc. Co-extruded, multi-lumen medical lead
GB2399309A (en) * 2001-12-19 2004-09-15 Advanced Bio Surfaces Inc Bone smoothing method and system
JP4324478B2 (en) * 2002-01-22 2009-09-02 アドバンスト バイオ サーフェイシズ，インコーポレイティド Interposition arthroplasty system
ES2309350T3 (en) * 2002-07-11 2008-12-16 Advanced Bio Surfaces, Inc. METHOD AND EQUIPMENT FOR INTERPOSITIONAL ARTROPLASTY.
DE10243966A1 (en) * 2002-09-20 2004-04-01 Adiam Life Science Ag Process for the production of biocompatible polyurethanes
DE10243965A1 (en) * 2002-09-20 2004-04-01 Adiam Life Science Ag Process for the production of biocompatible polyurethanes
TW200533385A (en) * 2004-03-03 2005-10-16 Commw Scient Ind Res Org Biocompatible polymer compositions for dual or multi staged curing
US20060282169A1 (en) * 2004-12-17 2006-12-14 Felt Jeffrey C System and method for upper extremity joint arthroplasty
KR20070101239A (en) * 2005-01-08 2007-10-16 알파스파인, 아이엔씨. Modular disk device
US7267690B2 (en) * 2005-03-09 2007-09-11 Vertebral Technologies, Inc. Interlocked modular disc nucleus prosthesis
CN101296958B (en) 2005-09-20 2012-07-18 宝利诺沃生物材料有限公司 Chain extenders
EP2049591A4 (en) * 2006-08-02 2009-08-19 Polynovo Biomaterials Pty Ltd Biocompatible polymer compositions
US9737414B2 (en) 2006-11-21 2017-08-22 Vertebral Technologies, Inc. Methods and apparatus for minimally invasive modular interbody fusion devices
DE102007033787A1 (en) 2007-07-09 2009-01-15 Aesculap Ag Vascular prosthesis with reduced thrombogenicity
AU2008307139B2 (en) * 2007-10-03 2012-12-20 Polynovo Biomaterials Pty Limited High modulus polyurethane and polyurethane/urea compositions
DE102007061301A1 (en) 2007-12-10 2009-06-18 Aesculap Ag Sheath to restore the valve function of varicose veins and use of the sheath in surgery
KR101464983B1 (en) * 2008-05-01 2014-11-25 스파인셀 프러프라이어테리 리미티드 System methods and apparatuses for formation and insertion of tissue prothesis
EP2291206A2 (en) * 2008-05-19 2011-03-09 Orteq B.V. Polyurethane foam for use in medical implants
EP2156853A1 (en) 2008-08-19 2010-02-24 Aesculap AG Medical product for treatment of sinusitis
BR112012030702A2 (en) 2010-06-02 2017-06-13 Nonwotecc Medial Gmbh device for positioning a hollow organ, in particular for keeping said hollow organ open and method for producing such a device
ES2734888T3 (en) 2010-09-06 2019-12-12 Occlutech Holding Ag Device for closing openings or cavities in blood vessels
DE102011000400A1 (en) 2011-01-28 2012-08-02 Aesculap Ag Conduit-valve prosthesis e.g. conduit-cardiac valve prosthesis, for e.g. replacing deflective aorta valve for patient, has cusps formed at bulb-like projections of body, where prosthesis is integrally formed based on polyurethane-material
US9510953B2 (en) 2012-03-16 2016-12-06 Vertebral Technologies, Inc. Modular segmented disc nucleus implant

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3239318A1 (en) * 1981-10-30 1983-05-11 Thermo Electron Corp., 02154 Waltham, Mass. MOLDABLE POLYURETHANE ELASTOMER WITH GOOD BLOOD COMPATIBILITY

Family Cites Families (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3351650A (en) * 1963-11-26 1967-11-07 Mobay Chemical Corp 2, 4-and 2, 6-lower alkyl cyclohexylene diisocyanate mixtures
DE1694080B1 (en) * 1966-10-13 1971-09-30 Bayer Ag PROCESS FOR THE PRODUCTION OF CROSS-LINKED POLYURETHANES ON THE BASIS OF HYDROXYL POLYCARBON EASTERS
US3590002A (en) * 1967-07-21 1971-06-29 Mobay Chemical Corp Mixtures of 2,4'-diisocyanato dicyclohexylmethane with lower aliphatic and cycloaliphatic polyisocyanates
GB1240116A (en) * 1968-06-07 1971-07-21 Ici Ltd Improvements in or relating to the manufacture of synthetic elastomers
US3620905A (en) * 1969-10-21 1971-11-16 Du Pont Optically clear thermoplastic polyurethanes
US3870683A (en) * 1970-11-12 1975-03-11 Gulf Oil Canada Ltd Light stable polyurethanes based on dicyclohexyl and diisocyanates
BE792203A (en) * 1971-08-02 1973-06-01 Ppg Industries Inc SHEET PRODUCTS WITH GOOD IMPACT RESISTANCE
US3769162A (en) * 1971-08-26 1973-10-30 R Brumfield Blood oxygenator and thermoregulator apparatus
US3879516A (en) * 1972-12-07 1975-04-22 Technibiotics Method of constructing a catheter
US3897401A (en) * 1974-03-25 1975-07-29 Goodyear Tire & Rubber Liquid polyurethane reaction mixture
DE2432090C2 (en) * 1974-07-04 1982-02-11 Fa. Carl Freudenberg, 6940 Weinheim Elastic molding compound based on polyurethane
PL104172B1 (en) * 1975-12-31 1979-08-31 AN ARTIFICIAL HEART MOVED BY BREATHING MONTHS
DE2614243C2 (en) * 1976-04-02 1982-10-07 Bayer Ag, 5090 Leverkusen Cycloaliphatic triisocyanates, process for their preparation and their use
DE2622502A1 (en) * 1976-05-20 1977-11-24 Rehau Plastiks Polyvinyl chloride test tubes, e.g. for dialysis - which are coated internally with a transparent, plasticiser-free layer of thermoplastic (NL 22.11.77)
US4180896A (en) * 1977-12-29 1980-01-01 Texas Medical Products, Inc. Blood oxygenator assembly method
US4224432A (en) * 1978-12-11 1980-09-23 E. I. Du Pont De Nemours And Company Polyurethanes prepared with tetrahydrofuran-alkylene oxide polymerizates having low oligomeric cyclic ether content
DE2813197C2 (en) * 1978-03-25 1983-09-08 Akzo Gmbh, 5600 Wuppertal Embedding material, process for its manufacture and its use
DE2829199A1 (en) * 1978-07-03 1980-02-21 Akzo Gmbh POLYURETHANE FROM TRANS-CYCLOHEXANE-1,4-DIISOCYANATE
US4284506A (en) * 1979-12-26 1981-08-18 Nl Industries, Inc. Biomedical devices
DE3127464C2 (en) * 1981-07-11 1986-10-30 Akzo Gmbh, 5600 Wuppertal Linear segmented polyurethanes and processes for their manufacture
JPS58502211A (en) * 1981-08-26 1983-12-22 メリル，エドワ−ド　ダブリユ− Segmented polyurethane composition
DE3147025A1 (en) * 1981-11-27 1983-06-01 Akzo Gmbh, 5600 Wuppertal EMBEDDING BASED ON QUICK REACTIVE POLYURETHANE CASTING RESIN
US4476293A (en) * 1981-11-30 1984-10-09 E. I. Du Pont De Nemours And Company Polymeric carbonate diols of copolyether glycols and polyurethanes prepared therefrom
DE3149527A1 (en) * 1981-12-14 1983-06-23 VEB Synthesewerk Schwarzheide Kombinat SYS, DDR 7817 Schwarzheide Polyurethane compositions for hollow fibre dialysers
JPS58185647A (en) * 1982-03-17 1983-10-29 Nippon Zeon Co Ltd Stable polymer emulsion composition giving antithrombotic surface and preparation thereof
DE8301959U1 (en) * 1983-01-21 1983-05-26 Buecherl, Emil,Sebastian, Prof.Dr.Med., 1000 Berlin, De
IT1169561B (en) * 1983-09-13 1987-06-03 Matec Holding Ag PROCEDURE FOR OBTAINING WITH A SINGLE MOLDING OPERATION OF DOUBLE WALL STRUCTURES FOR SOUNDPROOFING OF VEHICLES AND ENGINES IN GENERAL AND DOUBLE WALL STRUCTURE OBTAINED BY SUCH PROCEDURE
US4816529A (en) * 1985-11-18 1989-03-28 The Dow Chemical Company Novel ester-modified poly(alkylene carbonate) polyahls and polyurethanes therefrom
US4861909A (en) * 1986-04-11 1989-08-29 The Dow Chemical Company Isocyanate-modified poly(alkylene carbonate) polyahls
US5001208A (en) * 1989-03-20 1991-03-19 Reeves Brothers, Inc. Linear polyurethane elastomer compositions based on mixed polycarbonate and polyether polyols

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3239318A1 (en) * 1981-10-30 1983-05-11 Thermo Electron Corp., 02154 Waltham, Mass. MOLDABLE POLYURETHANE ELASTOMER WITH GOOD BLOOD COMPATIBILITY

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US5109077A (en) 1992-04-28
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DE3318730A1 (en) 1984-11-22
IT8448218A0 (en) 1984-05-18
JPH0410892B2 (en) 1992-02-26
FR2546170B1 (en) 1987-06-12
DE3318730C2 (en) 1990-06-21

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